Ua tsaug rau koj tuaj xyuas Nature.com. Lub browser version uas koj siv muaj kev txhawb nqa CSS tsawg. Rau qhov zoo tshaj plaws, peb xav kom siv lub browser version tshiab dua (lossis tua hom kev sib raug zoo hauv Internet Explorer). Lub sijhawm no, kom ntseeg tau tias muaj kev txhawb nqa tas mus li, peb tab tom qhia lub xaib yam tsis muaj styling lossis JavaScript.
Kev ua kom tsis zoo tau siv dav los txhim kho kev ua haujlwm ntawm cov roj teeb hnub ci triiodide perovskite, tab sis qhov cuam tshuam ntawm ntau yam tsis zoo ntawm α-theem ruaj khov tseem tsis meej; Ntawm no, siv cov kev xav ua haujlwm ceev, peb txheeb xyuas thawj zaug txoj kev puas tsuaj ntawm formamidine lead triiodide perovskite los ntawm α-theem mus rau δ-theem thiab kawm txog qhov cuam tshuam ntawm ntau yam tsis zoo ntawm lub zog hloov pauv theem. Cov txiaj ntsig simulation kwv yees tias cov chaw tsis muaj iodine feem ntau yuav ua rau muaj kev puas tsuaj vim tias lawv txo qis lub zog thaiv rau α-δ theem hloov pauv thiab muaj lub zog tsim qis tshaj plaws ntawm qhov chaw perovskite. Kev qhia txog ib txheej tuab ntawm cov hlau lead oxalate uas tsis yaj hauv dej rau ntawm qhov chaw perovskite ua rau muaj kev puas tsuaj ntawm α-theem, tiv thaiv kev tsiv teb tsaws chaw thiab volatilization ntawm iodine. Tsis tas li ntawd, txoj kev no txo ​​​​​​qhov sib xyaw ua ke ntawm cov tshuaj tsis muaj hluav taws xob thiab ua rau lub zog ua haujlwm ntawm lub roj teeb hnub ci nce mus txog 25.39% (tau ntawv pov thawj 24.92%). Lub cuab yeej uas tsis tau ntim khoom tseem tuaj yeem khaws nws qhov ua tau zoo li qub 92% tom qab ua haujlwm ntawm lub zog siab tshaj plaws rau 550 teev nyob rau hauv kev simulated 1.5 G huab cua irradiation.
Qhov ua tau zoo ntawm kev hloov pauv hluav taws xob (PCE) ntawm cov roj teeb hnub ci perovskite (PSCs) tau mus txog qhov siab tshaj plaws ntawm 26%1. Txij li xyoo 2015, PSCs niaj hnub no tau nyiam formamidine triiodide perovskite (FAPbI3) ua ib txheej uas nqus tau lub teeb vim nws qhov kev ruaj khov thermal zoo heev thiab qhov bandgap nyiam ze rau Shockley-Keisser txwv ntawm 2,3,4. Hmoov tsis zoo, cov yeeb yaj kiab FAPbI3 thermodynamically dhau los ntawm kev hloov pauv theem los ntawm theem dub α mus rau theem daj tsis yog perovskite δ ntawm chav sov5,6. Txhawm rau tiv thaiv kev tsim ntawm theem delta, ntau yam kev sib xyaw ua ke perovskite tau tsim. Txoj kev siv ntau tshaj plaws los daws qhov teeb meem no yog sib tov FAPbI3 nrog kev sib xyaw ntawm methyl ammonium (MA +), cesium (Cs +) thiab bromide (Br-) ions7,8,9. Txawm li cas los xij, hybrid perovskites raug kev txom nyem los ntawm bandgap broadening thiab photoinduced phase separation, uas ua rau muaj kev cuam tshuam rau kev ua haujlwm thiab kev ruaj khov ntawm cov PSCs10,11,12.
Cov kev tshawb fawb tsis ntev los no tau qhia tias cov khoom siv lead ua ib leeg FAPbI3 uas tsis muaj doping muaj kev ruaj khov zoo heev vim nws qhov crystallinity zoo heev thiab qhov tsis zoo tsawg13,14. Yog li ntawd, txo qhov tsis zoo los ntawm kev nce qhov crystallinity ntawm cov FAPbI3 loj yog ib qho tseem ceeb kom ua tiav PSCs zoo thiab ruaj khov2,15. Txawm li cas los xij, thaum lub sijhawm ua haujlwm ntawm FAPbI3 PSC, kev puas tsuaj rau qhov tsis xav tau daj hexagonal tsis yog perovskite δ theem tseem tuaj yeem tshwm sim16. Cov txheej txheem feem ntau pib ntawm cov chaw thiab cov ciam teb ntawm cov noob uas yooj yim rau dej, cua sov thiab lub teeb vim muaj ntau qhov chaw tsis zoo17. Yog li ntawd, qhov chaw / noob passivation yog qhov tsim nyog los tswj cov theem dub ntawm FAPbI318. Ntau txoj kev kho qhov tsis zoo, suav nrog kev qhia txog cov perovskites qis-dimensional, acid-base Lewis molecules, thiab ammonium halide ntsev, tau ua tiav zoo hauv formamidine PSCs19,20,21,22. Txog niaj hnub no, yuav luag txhua txoj kev tshawb fawb tau tsom mus rau lub luag haujlwm ntawm ntau yam kev tsis zoo hauv kev txiav txim siab txog cov khoom siv optoelectronic xws li kev sib xyaw ua ke ntawm cov neeg nqa khoom, qhov ntev ntawm kev sib kis thiab cov qauv ntawm cov kab hauv cov hnub ci cell22,23,24. Piv txwv li, kev tshawb fawb txog kev ua haujlwm ntawm qhov ceev (DFT) yog siv los kwv yees qhov kev tsim lub zog thiab kev ntes cov qib zog ntawm ntau yam kev tsis zoo, uas yog siv dav los coj kev tsim qauv passivation20,25,26. Raws li tus lej ntawm cov kev tsis zoo txo ​​qis, qhov ruaj khov ntawm lub cuab yeej feem ntau txhim kho. Txawm li cas los xij, hauv formamidine PSCs, cov txheej txheem ntawm kev cuam tshuam ntawm ntau yam kev tsis zoo ntawm kev ruaj khov theem thiab cov khoom photoelectric yuav tsum txawv kiag li. Raws li peb qhov kev paub zoo tshaj plaws, qhov kev nkag siab tseem ceeb ntawm yuav ua li cas cov kev tsis zoo ua rau lub cubic mus rau hexagonal (α-δ) theem hloov pauv thiab lub luag haujlwm ntawm qhov chaw passivation ntawm theem ruaj khov ntawm α-FAPbI3 perovskite tseem tsis tau nkag siab zoo.
Ntawm no, peb qhia txog txoj kev puas tsuaj ntawm FAPbI3 perovskite los ntawm α-theem dub mus rau δ-theem daj thiab qhov cuam tshuam ntawm ntau yam tsis zoo ntawm lub zog thaiv ntawm α-rau-δ-theem hloov pauv ntawm DFT. Kuv qhov chaw khoob, uas yooj yim tsim thaum lub sijhawm tsim zaj duab xis thiab kev ua haujlwm ntawm lub cuab yeej, kwv yees tias yuav muaj feem ntau pib qhov kev hloov pauv theem α-δ. Yog li ntawd, peb tau qhia txog cov txheej txheem ntom ntom ntawm cov hlau lead oxalate (PbC2O4) uas tsis yaj hauv dej thiab ruaj khov hauv tshuaj lom neeg rau saum FAPbI3 los ntawm kev ua haujlwm hauv qhov chaw. Cov hlau lead oxalate nto (LOS) tiv thaiv kev tsim cov chaw khoob I thiab tiv thaiv kev tsiv teb tsaws chaw ntawm I ions thaum raug txhawb los ntawm cua sov, lub teeb, thiab cov teb hluav taws xob. Qhov tshwm sim LOS txo qis kev sib xyaw ua ke ntawm cov tshuaj tsis muaj hluav taws xob thiab txhim kho FAPbI3 PSC kev ua haujlwm mus rau 25.39% (tau ntawv pov thawj rau 24.92%). Lub cuab yeej LOS uas tsis tau ntim khoom khaws cia 92% ntawm nws qhov kev ua haujlwm zoo thawj zaug tom qab ua haujlwm ntawm qhov chaw muaj zog tshaj plaws (MPP) rau ntau tshaj 550 teev ntawm qhov hnyav huab cua simulated (AM) ntawm 1.5 G ntawm hluav taws xob.
Peb thawj zaug ua qhov kev xam ab initio kom nrhiav tau txoj kev rhuav tshem ntawm FAPbI3 perovskite kom hloov pauv ntawm theem α mus rau theem δ. Los ntawm cov txheej txheem hloov pauv theem ntxaws ntxaws, nws pom tias kev hloov pauv los ntawm peb-seem ces kaum-sib koom [PbI6] octahedron hauv cubic α-theem ntawm FAPbI3 mus rau ib-seem ntug-sib koom [PbI6] octahedron hauv hexagonal δ-theem ntawm FAPbI3 tau ua tiav. tawg 9. Pb-I tsim ib daim ntawv cog lus hauv thawj kauj ruam (Int-1), thiab nws lub zog thaiv ncav cuag 0.62 eV / cell, raws li pom hauv Daim Duab 1a. Thaum lub octahedron raug hloov mus rau hauv [0\(\bar{1}\)1] kev taw qhia, lub hexagonal luv saw nthuav dav los ntawm 1 × 1 mus rau 1 × 3, 1 × 4 thiab thaum kawg nkag mus rau theem δ. Qhov piv ntawm kev taw qhia ntawm tag nrho txoj kev yog (011)α//(001)δ + [100]α//[100]δ. Los ntawm daim duab faib hluav taws xob, nws tuaj yeem pom tias tom qab nucleation ntawm δ theem ntawm FAPbI3 hauv cov theem hauv qab no, lub zog thaiv qis dua li ntawm α theem hloov pauv, uas txhais tau tias qhov kev hloov pauv theem yuav raug ua kom nrawm dua. Nws yog qhov tseeb, thawj kauj ruam ntawm kev tswj hwm qhov kev hloov pauv theem yog qhov tseem ceeb yog tias peb xav kom tsis txhob muaj kev puas tsuaj α-theem.
a Cov txheej txheem hloov pauv theem ntawm sab laug mus rau sab xis - theem dub FAPbI3 (α-theem), thawj Pb-I bond cleavage (Int-1) thiab ntxiv Pb-I bond cleavage (Int-2, Int -3 thiab Int -4) thiab theem daj FAPbI3 (delta theem). b Cov teeb meem zog rau α mus rau δ theem hloov pauv ntawm FAPbI3 raws li ntau yam intrinsic point defects. Cov kab dotted qhia txog lub zog barrier ntawm ib qho crystal zoo tagnrho (0.62 eV). c Lub zog ntawm kev tsim cov ntsiab lus tseem ceeb ntawm qhov chaw ntawm lead perovskite. Lub abscissa axis yog lub zog barrier ntawm α-δ theem hloov pauv, thiab lub ordinate axis yog lub zog ntawm kev tsim qhov tsis zoo. Cov khoom uas ntxoov ntxoo hauv grey, daj thiab ntsuab yog hom I (EB qis-FE siab), hom II (FE siab) thiab hom III (EB qis-FE qis), raws li. d Lub zog ntawm kev tsim cov qhov tsis zoo VI thiab LOS ntawm FAPbI3 hauv kev tswj hwm. e I teeb meem rau ion migration hauv kev tswj hwm thiab LOS ntawm FAPbI3. f - daim duab qhia txog kev tsiv teb tsaws chaw ntawm I ions (cov pob zeb txiv kab ntxwv) thiab gLOS FAPbI3 (grey, lead; violet (txiv kab ntxwv), iodine (mobile iodine)) hauv gf tswj (sab laug: saib sab saud; sab xis: seem hla, xim av); carbon; xiav daj - nitrogen; liab - oxygen; liab dawb - hydrogen). Cov ntaub ntawv qhov chaw tau muab los ua cov ntaub ntawv qhov chaw.
Tom qab ntawd peb tau kawm txog kev cuam tshuam ntawm ntau yam teeb meem intrinsic point defects (xws li PbFA, IFA, PbI, thiab IPb antisite occupancy; Pbi thiab Ii interstitial atoms; thiab VI, VFA, thiab VPb vacancies), uas suav hais tias yog cov yam tseem ceeb. uas ua rau atomic thiab theem zog degradation tau pom hauv Daim Duab 1b thiab Cov Lus Qhia Ntxiv 1. Qhov nthuav yog, tsis yog txhua qhov teeb meem txo qhov teeb meem zog ntawm α-δ theem hloov pauv (Daim Duab 1b). Peb ntseeg tias qhov teeb meem uas muaj ob qho tib si qis tsim zog thiab qis dua α-δ theem hloov pauv zog teeb meem raug suav hais tias ua rau muaj kev ruaj khov theem. Raws li tau tshaj tawm ua ntej, cov nplaim nplua nuj lead feem ntau suav hais tias zoo rau formamidine PSC27. Yog li ntawd, peb tsom mus rau PbI2-terminated (100) nto nyob rau hauv cov xwm txheej nplua nuj lead. Lub zog tsim teeb meem ntawm qhov chaw intrinsic point defects tau pom hauv Daim Duab 1c thiab Cov Lus Qhia Ntxiv 1. Raws li lub zog thaiv (EB) thiab theem hloov pauv tsim zog (FE), cov teeb meem no tau muab faib ua peb hom. Hom I (EB qis-FE siab): Txawm hais tias IPb, VFA thiab VPb txo qhov kev cuam tshuam zog rau kev hloov pauv theem, lawv muaj lub zog tsim siab. Yog li ntawd, peb ntseeg tias cov hom kev tsis zoo no muaj kev cuam tshuam tsawg rau kev hloov pauv theem vim tias lawv tsis tshua muaj. Hom II (EB siab): Vim yog qhov kev txhim kho α-δ theem kev hloov pauv zog, qhov tsis zoo tiv thaiv qhov chaw PbI, IFA thiab PbFA tsis ua rau puas tsuaj rau theem kev ruaj khov ntawm α-FAPbI3 perovskite. Hom III (EB qis-FE qis): VI, Ii thiab Pbi qhov tsis zoo nrog lub zog tsim qis tuaj yeem ua rau muaj kev puas tsuaj theem dub. Tshwj xeeb tshaj yog muab qhov qis tshaj plaws FE thiab EB VI, peb ntseeg tias qhov zoo tshaj plaws yog txo I qhov chaw seem.
Yuav kom txo tau VI, peb tau tsim ib txheej tuab ntawm PbC2O4 los txhim kho qhov chaw ntawm FAPbI3. Piv rau cov organic halide ntsev passivators xws li phenylethylammonium iodide (PEAI) thiab n-octylammonium iodide (OAI), PbC2O4, uas tsis muaj cov halogen ions txawb, yog cov tshuaj ruaj khov, tsis yaj hauv dej, thiab yooj yim deactivated thaum muaj kev txhawb nqa. Kev ruaj khov zoo ntawm qhov chaw noo noo thiab lub zog hluav taws xob ntawm perovskite. Qhov solubility ntawm PbC2O4 hauv dej tsuas yog 0.00065 g / L, uas qis dua li ntawm PbSO428. Qhov tseem ceeb tshaj plaws, cov khaubncaws sab nraud povtseg tuab thiab sib xws ntawm LOS tuaj yeem npaj tau yooj yim ntawm cov yeeb yaj kiab perovskite siv cov tshuaj tiv thaiv hauv qhov chaw (saib hauv qab no). Peb tau ua DFT simulations ntawm kev sib txuas ntawm FAPbI3 thiab PbC2O4 raws li pom hauv Daim Duab Ntxiv 1. Daim Ntawv Ntxiv 2 qhia txog lub zog tsim qhov tsis zoo tom qab LOS txhaj tshuaj. Peb pom tias LOS tsis yog tsuas yog ua rau lub zog tsim ntawm VI defects los ntawm 0.69–1.53 eV (Daim Duab 1d), tab sis kuj ua rau lub zog ua haujlwm ntawm I ntawm qhov chaw tsiv teb tsaws chaw thiab qhov chaw tawm (Daim Duab 1e). Hauv thawj theem, I ions tsiv teb tsaws chaw raws perovskite nto, tawm hauv VI ions nyob rau hauv txoj haujlwm lattice nrog lub zog thaiv ntawm 0.61 eV. Tom qab kev qhia ntawm LOS, vim yog qhov cuam tshuam ntawm steric hindrance, lub zog ua haujlwm rau kev tsiv teb tsaws chaw ntawm I ions nce mus rau. 1.28 eV. Thaum lub sijhawm tsiv teb tsaws chaw ntawm I ions tawm ntawm perovskite nto, lub zog thaiv hauv VOC kuj siab dua li hauv cov qauv tswj (Daim Duab 1e). Cov duab kos ntawm I ion migration pathways hauv kev tswj thiab LOS FAPbI3 tau qhia hauv Daim Duab 1 f thiab g, feem. Cov txiaj ntsig simulation qhia tau tias LOS tuaj yeem tiv thaiv kev tsim ntawm VI defects thiab volatilization ntawm I, yog li tiv thaiv kev hloov pauv ntawm α rau δ theem.
Qhov kev tshuaj tiv thaiv ntawm oxalic acid thiab FAPbI3 perovskite tau sim. Tom qab sib tov cov tshuaj ntawm oxalic acid thiab FAPbI3, ntau cov av dawb tau tsim, raws li pom hauv Daim Duab Ntxiv 2. Cov khoom hmoov tau txheeb xyuas tias yog cov khoom siv PbC2O4 ntshiab siv X-ray diffraction (XRD) (Daim Duab Ntxiv 3) thiab Fourier hloov infrared spectroscopy (FTIR) (Daim Duab Ntxiv 4). Peb pom tias oxalic acid yaj tau zoo heev hauv isopropyl cawv (IPA) ntawm chav tsev kub nrog kev yaj ntawm kwv yees li 18 mg / mL, raws li pom hauv Daim Duab Ntxiv 5. Qhov no ua rau kev ua tiav tom qab yooj yim dua vim IPA, ua cov kuab tshuaj passivation, tsis ua puas rau txheej perovskite dhau lub sijhawm luv luv 29. Yog li ntawd, los ntawm kev muab cov zaj duab xis perovskite tso rau hauv cov kua oxalic acid lossis kev sib xyaw cov kua oxalic acid rau ntawm perovskite, PbC2O4 nyias thiab ntom tuaj yeem tau txais sai sai ntawm qhov chaw ntawm cov zaj duab xis perovskite raws li cov qauv tshuaj lom neeg hauv qab no: H2C2O4 + FAPbI3 = PbC2O4 + FAI +HI. FAI tuaj yeem yaj hauv IPA thiab yog li tshem tawm thaum lub sijhawm ua noj. Qhov tuab ntawm LOS tuaj yeem tswj tau los ntawm lub sijhawm teb thiab cov khoom siv ua ntej.
Cov duab thaij duab electron microscopy (SEM) ntawm kev tswj hwm thiab LOS perovskite zaj duab xis tau pom hauv Daim Duab 2a, b. Cov txiaj ntsig qhia tau tias qhov morphology ntawm perovskite nto tau khaws cia zoo, thiab muaj ntau cov khoom me me tau tso rau ntawm qhov chaw ntawm cov noob, uas yuav tsum sawv cev rau txheej PbC2O4 uas tsim los ntawm qhov tshuaj tiv thaiv hauv-situ. Zaj duab xis LOS perovskite muaj qhov chaw du me ntsis (Daim Duab Ntxiv 6) thiab lub kaum sab xis dej loj dua piv rau zaj duab xis tswj hwm (Daim Duab Ntxiv 7). Kev siv tshuab hluav taws xob transverse transmission high-resolution (HR-TEM) tau siv los cais qhov txheej ntawm cov khoom. Piv rau zaj duab xis tswj hwm (Daim Duab 2c), ib txheej nyias nyias thiab tuab nrog qhov tuab ntawm kwv yees li 10 nm pom tseeb rau saum LOS perovskite (Daim Duab 2d). Siv lub tshuab ntsuas hluav taws xob scanning electron microscopy (HAADF-STEM) uas muaj lub kaum sab xis siab (HAADF-STEM) los tshuaj xyuas qhov sib txuas ntawm PbC2O4 thiab FAPbI3, qhov muaj cov cheeb tsam crystalline ntawm FAPbI3 thiab cov cheeb tsam amorphous ntawm PbC2O4 tuaj yeem pom tseeb (Daim Duab Ntxiv 8). Cov khoom sib xyaw ntawm perovskite tom qab kev kho mob oxalic acid tau piav qhia los ntawm kev ntsuas X-ray photoelectron spectroscopy (XPS), raws li pom hauv Daim Duab 2e-g. Hauv Daim Duab 2e, C 1s nce mus txog 284.8 eV thiab 288.5 eV koom nrog cov teeb liab CC thiab FA tshwj xeeb, feem. Piv rau daim nyias nyias tswj, daim nyias nyias LOS tau pom qhov nce ntxiv ntawm 289.2 eV, uas yog vim C2O42-. Cov O 1s spectrum ntawm LOS perovskite qhia txog peb qhov sib txawv ntawm cov tshuaj O 1s peaks ntawm 531.7 eV, 532.5 eV, thiab 533.4 eV, sib raug rau deprotonated COO, C = O ntawm cov pab pawg oxalate 30 thiab O atoms ntawm OH Cheebtsam (Daim Duab 2e). )). Rau cov qauv tswj, tsuas yog pom ib qho me me ntawm O 1s peak, uas tuaj yeem yog vim cov pa oxygen chemisorbed ntawm qhov chaw. Cov yam ntxwv ntawm daim nyias nyias tswj ntawm Pb 4f7 / 2 thiab Pb 4f5 / 2 nyob ntawm 138.4 eV thiab 143.3 eV, feem. Peb tau pom tias LOS perovskite qhia txog kev hloov pauv ntawm Pb peak ntawm kwv yees li 0.15 eV mus rau lub zog khi siab dua, qhia txog kev sib cuam tshuam muaj zog ntawm C2O42- thiab Pb atoms (Daim Duab 2g).
a cov duab SEM ntawm kev tswj thiab b LOS perovskite zaj duab xis, saib sab saud. c High-resolution cross-sectional transmission electron microscopy (HR-TEM) ntawm kev tswj thiab d LOS perovskite zaj duab xis. High-resolution XPS ntawm e C 1s, f O 1s thiab g Pb 4f perovskite zaj duab xis. Cov ntaub ntawv qhov chaw yog muab los ntawm cov ntaub ntawv qhov chaw.
Raws li cov txiaj ntsig DFT, nws yog qhov kwv yees tias VI qhov tsis zoo thiab I kev tsiv teb tsaws chaw yooj yim ua rau theem hloov pauv ntawm α mus rau δ. Cov ntawv ceeb toom yav dhau los tau qhia tias I2 raug tso tawm sai sai los ntawm PC-based perovskite zaj duab xis thaum lub sijhawm photoimmersion tom qab qhia cov zaj duab xis rau lub teeb thiab thermal stress31,32,33. Txhawm rau kom paub meej tias qhov stabilizing effect ntawm lead oxalate ntawm α-theem ntawm perovskite, peb tau muab cov yeeb yaj kiab tswj thiab LOS perovskite rau hauv lub raj mis iav pob tshab uas muaj toluene, feem, thiab tom qab ntawd irradiated lawv nrog 1 lub hnub ci rau 24 teev. Peb ntsuas qhov nqus ntawm ultraviolet thiab pom lub teeb (UV-Vis).) toluene kua, raws li pom hauv Daim Duab 3a. Piv nrog cov qauv tswj, qhov qis dua I2 nqus tau pom hauv rooj plaub ntawm LOS-perovskite, qhia tias compact LOS tuaj yeem tiv thaiv kev tso tawm ntawm I2 los ntawm perovskite zaj duab xis thaum lub sijhawm lub teeb immersion. Cov duab ntawm cov laus tswj thiab LOS perovskite zaj duab xis tau pom hauv cov duab ntawm Daim Duab 3b thiab c. Lub LOS perovskite tseem dub, thaum feem ntau ntawm cov yeeb yaj kiab tswj tau tig daj. Cov UV-pom kev nqus spectra ntawm cov yeeb yaj kiab immersed tau qhia nyob rau hauv Figs. 3b, c. Peb pom tias qhov kev nqus sib raug rau α hauv cov yeeb yaj kiab tswj tau txo qis. Kev ntsuas X-ray tau ua los sau cov ntaub ntawv ntawm cov qauv siv lead ua. Tom qab 24 teev ntawm kev ci ntsa iab, cov perovskite tswj tau qhia txog lub teeb liab daj δ-theem muaj zog (11.8 °), thaum LOS perovskite tseem tswj tau qhov theem dub zoo (Daim Duab 3d).
Cov duab nqus dej ntawm cov tshuaj toluene uas pom tau los ntawm UV uas cov yeeb yaj kiab tswj thiab cov yeeb yaj kiab LOS tau muab tso rau hauv qab hnub ci 1 teev rau 24 teev. Daim duab ntxig qhia txog lub raj mis uas txhua zaj yeeb yaj kiab tau muab tso rau hauv qhov sib npaug ntawm toluene. b Cov duab nqus dej UV-Vis ntawm cov yeeb yaj kiab tswj thiab c LOS zaj duab xis ua ntej thiab tom qab 24 teev ntawm kev muab tso rau hauv qab hnub ci 1 teev. Daim duab ntxig qhia txog daim duab ntawm zaj duab xis sim. d Cov qauv X-ray diffraction ntawm cov yeeb yaj kiab tswj thiab LOS ua ntej thiab tom qab 24 teev ntawm kev raug tshuaj. Cov duab SEM ntawm zaj duab xis tswj e thiab zaj duab xis f LOS tom qab 24 teev ntawm kev raug tshuaj. Cov ntaub ntawv qhov chaw tau muab los ua cov ntaub ntawv qhov chaw.
Peb tau ua qhov kev ntsuas scanning electron microscopy (SEM) los soj ntsuam cov kev hloov pauv microstructural ntawm perovskite zaj duab xis tom qab 24 teev ntawm lub teeb, raws li pom hauv Daim Duab 3e, f. Hauv zaj duab xis tswj, cov noob loj tau raug rhuav tshem thiab tig mus rau hauv cov koob me me, uas sib raug rau cov morphology ntawm δ-theem khoom FAPbI3 (Daim Duab 3e). Rau LOS zaj duab xis, cov noob perovskite tseem nyob rau hauv qhov zoo (Daim Duab 3f). Cov txiaj ntsig tau lees paub tias qhov poob ntawm I ua rau muaj kev hloov pauv ntawm theem dub mus rau theem daj, thaum PbC2O4 tswj cov theem dub, tiv thaiv kev poob ntawm I. Txij li thaum qhov chaw khoob ntawm qhov chaw siab dua li hauv cov noob loj,34 theem no yuav tshwm sim ntau dua ntawm qhov chaw ntawm cov noob. tib lub sijhawm tso iodine thiab tsim VI. Raws li DFT kwv yees, LOS tuaj yeem tiv thaiv kev tsim cov VI tsis zoo thiab tiv thaiv kev tsiv teb tsaws chaw ntawm I ions mus rau qhov chaw perovskite.
Tsis tas li ntawd xwb, cov nyhuv ntawm PbC2O4 txheej rau qhov tsis kam ntawm cov dej noo ntawm cov yeeb yaj kiab perovskite hauv huab cua (qhov av noo kwv yees li 30-60%) tau kawm. Raws li pom hauv Daim Duab Ntxiv 9, LOS perovskite tseem dub tom qab 12 hnub, thaum cov yeeb yaj kiab tswj tau tig daj. Hauv kev ntsuas XRD, cov yeeb yaj kiab tswj qhia txog qhov siab tshaj plaws ntawm 11.8 ° sib raug rau theem δ ntawm FAPbI3, thaum LOS perovskite khaws cia qhov dub α theem zoo (Daim Duab Ntxiv 10).
Cov duab ci ntsa iab ruaj khov (PL) thiab cov duab ci ntsa iab uas daws tau lub sijhawm (TRPL) tau siv los kawm txog qhov cuam tshuam ntawm cov hlau lead oxalate rau ntawm qhov chaw perovskite. Hauv daim duab 4a qhia tau hais tias zaj duab xis LOS tau nce qhov muaj zog ntawm PL. Hauv daim duab PL mapping, qhov muaj zog ntawm zaj duab xis LOS hla tag nrho thaj tsam ntawm 10 × 10 μm2 yog siab dua li ntawm zaj duab xis tswj (Daim duab ntxiv 11), qhia tias PbC2O4 sib npaug zos passivates zaj duab xis perovskite. Lub neej ntawm tus neeg nqa khoom yog txiav txim siab los ntawm kev kwv yees qhov lwj ntawm TRPL nrog ib qho kev ua haujlwm exponential (Daim duab 4b). Lub neej ntawm tus neeg nqa khoom ntawm zaj duab xis LOS yog 5.2 μs, uas ntev dua li zaj duab xis tswj nrog lub neej ntawm tus neeg nqa khoom ntawm 0.9 μs, qhia txog qhov txo qis ntawm qhov chaw tsis muaj hluav taws xob.
Cov PL thiab b-spectra ruaj khov ntawm PL ib ntus ntawm cov yeeb yaj kiab perovskite ntawm cov iav substrates. c SP nkhaus ntawm lub cuab yeej (FTO/TiO2/SnO2/perovskite/spiro-OMeTAD/Au). d EQE spectrum thiab Jsc EQE spectrum sib xyaw los ntawm lub cuab yeej ua haujlwm zoo tshaj plaws. d Kev vam khom ntawm lub teeb ci ntawm lub cuab yeej perovskite ntawm daim duab Voc. f Kev tshuaj xyuas MKRC ib txwm siv ITO/PEDOT:PSS/perovskite/PCBM/Au lub cuab yeej ntxuav qhov. VTFL yog qhov siab tshaj plaws ntawm lub cuab yeej sau ntxiab. Los ntawm cov ntaub ntawv no peb tau xam qhov ceev ntawm lub ntxiab (Nt). Cov ntaub ntawv qhov chaw tau muab rau hauv daim ntawv ntawm cov ntaub ntawv qhov chaw.
Txhawm rau kawm txog qhov cuam tshuam ntawm cov txheej txheem txhuas oxalate rau kev ua haujlwm ntawm lub cuab yeej, cov qauv sib cuag FTO / TiO2 / SnO2 / perovskite / spiro-OMeTAD / Au ib txwm muaj tau siv. Peb siv formamidine chloride (FACl) ua ib qho khoom ntxiv rau perovskite precursor es tsis txhob methylamine hydrochloride (MACl) kom ua tiav kev ua haujlwm zoo dua ntawm lub cuab yeej, vim tias FACl tuaj yeem muab cov khoom siv lead ua tau zoo dua thiab zam qhov sib txawv ntawm FAPbI335 (saib Cov Duab Ntxiv 1 thiab 2 rau kev sib piv ntxaws ntxaws). ). 12-14). IPA tau raug xaiv los ua cov tshuaj tua kab mob vim tias nws muab cov khoom siv lead ua tau zoo dua thiab kev taw qhia zoo dua hauv cov yeeb yaj kiab perovskite piv rau diethyl ether (DE) lossis chlorobenzene (CB) 36 (Cov Duab Ntxiv 15 thiab 16). Lub thickness ntawm PbC2O4 tau ua tib zoo optimized kom zoo sib npaug qhov tsis zoo passivation thiab them nqi thauj los ntawm kev kho qhov concentration ntawm oxalic acid (Daim Duab Ntxiv 17). Cov duab SEM hla ntawm cov khoom siv tswj hwm zoo tshaj plaws thiab LOS tau pom hauv Daim Duab Ntxiv 18. Cov kab nkhaus tam sim no (CD) rau kev tswj hwm thiab LOS cov khoom siv tau pom hauv Daim Duab 4c, thiab cov kev ntsuas rho tawm tau muab rau hauv Rooj Ntxiv 3. Kev ua haujlwm hloov pauv hluav taws xob siab tshaj plaws (PCE) tswj hlwb 23.43% (22.94%), Jsc 25.75 mA cm-2 (25.74 mA cm-2), Voc 1.16 V (1.16 V) thiab rov qab (rau pem hauv ntej) scan. Tus lej sau (FF) yog 78.40% (76.69%). PCE LOS PSC siab tshaj plaws yog 25.39% (24.79%), Jsc yog 25.77 mA cm-2, Voc yog 1.18 V, FF yog 83.50% (81.52%) los ntawm rov qab (rau pem hauv ntej Scan mus rau). Lub cuab yeej LOS tau ua tiav qhov kev ua tau zoo ntawm photovoltaic ntawm 24.92% hauv lub chaw kuaj photovoltaic thib peb uas ntseeg siab (Daim Duab Ntxiv 19). Qhov ua tau zoo ntawm quantum sab nraud (EQE) tau muab Jsc sib xyaw ua ke ntawm 24.90 mA cm-2 (tswj) thiab 25.18 mA cm-2 (LOS PSC), raws li, uas yog qhov zoo sib xws nrog Jsc ntsuas hauv tus qauv AM 1.5 G spectrum (Daim Duab 4d). ). Kev faib tawm ntawm PCE ntsuas rau kev tswj thiab LOS PSCs tau qhia hauv Daim Duab Ntxiv 20.
Raws li pom hauv Daim Duab 4e, kev sib raug zoo ntawm Voc thiab lub teeb ci tau suav los kawm txog qhov cuam tshuam ntawm PbC2O4 rau kev sib xyaw ua ke ntawm qhov chaw uas tau pab los ntawm lub cuab yeej LOS. Qhov nqes ntawm txoj kab haum rau lub cuab yeej LOS yog 1.16 kBT/sq, uas qis dua qhov nqes ntawm txoj kab haum rau lub cuab yeej tswj (1.31 kBT/sq), lees paub tias LOS muaj txiaj ntsig zoo rau kev tiv thaiv kev sib xyaw ua ke ntawm qhov chaw los ntawm cov tsiaj reptiles. Peb siv cov thev naus laus zis space charge current limiting (SCLC) los ntsuas qhov ntom ntawm cov yeeb yaj kiab perovskite los ntawm kev ntsuas qhov tsaus ntuj IV yam ntxwv ntawm lub cuab yeej qhov (ITO/PEDOT:PSS/perovskite/spiro-OMeTAD/Au) raws li pom hauv daim duab. 4f Qhia. Qhov ceev ntawm lub ntxiab yog xam los ntawm cov mis Nt = 2ε0εVTFL/eL2, qhov twg ε yog qhov sib piv dielectric constant ntawm perovskite zaj duab xis, ε0 yog dielectric constant ntawm lub tshuab nqus tsev, VTFL yog qhov limiting voltage rau kev sau lub ntxiab, e yog qhov them, L yog qhov tuab ntawm perovskite zaj duab xis (650 nm). Qhov ceev ntawm qhov tsis zoo ntawm lub cuab yeej VOC yog xam los ntawm 1.450 × 1015 cm–3, uas qis dua qhov ceev ntawm qhov tsis zoo ntawm lub cuab yeej tswj, uas yog 1.795 × 1015 cm–3.
Lub cuab yeej tsis tau ntim khoom raug sim ntawm qhov chaw muaj zog siab tshaj plaws (MPP) nyob rau hauv lub hnub ci tag nrho hauv qab nitrogen los tshuaj xyuas nws qhov kev ua haujlwm ruaj khov mus sij hawm ntev (Daim Duab 5a). Tom qab 550 teev, lub cuab yeej LOS tseem tswj tau 92% ntawm nws qhov ua tau zoo tshaj plaws, thaum lub cuab yeej tswj hwm qhov kev ua tau zoo tau poob qis mus rau 60% ntawm nws qhov kev ua tau zoo thawj zaug. Kev faib tawm ntawm cov ntsiab lus hauv lub cuab yeej qub tau ntsuas los ntawm lub sijhawm-ntawm-dav hlau theem nrab ion mass spectrometry (ToF-SIMS) (Daim Duab 5b, c). Kev sib sau ua ke ntawm iodine ntau tuaj yeem pom hauv thaj chaw tswj kub sab saud. Cov xwm txheej ntawm kev tiv thaiv roj inert tsis suav nrog cov yam ntxwv ua rau ib puag ncig puas tsuaj xws li dej noo thiab oxygen, qhia tias cov txheej txheem sab hauv (piv txwv li, ion migration) yog lub luag haujlwm. Raws li cov txiaj ntsig ToF-SIMS, I- thiab AuI2- ions tau pom hauv Au electrode, qhia txog kev sib kis ntawm I los ntawm perovskite mus rau Au. Lub zog teeb liab ntawm I- thiab AuI2- ions hauv lub cuab yeej tswj hwm yog kwv yees li 10 npaug siab dua li ntawm VOC qauv. Cov ntawv ceeb toom yav dhau los tau qhia tias ion permeation tuaj yeem ua rau kom txo qis sai ntawm qhov conductivity ntawm spiro-OMeTAD thiab tshuaj xeb ntawm cov txheej electrode sab saum toj, yog li ua rau qhov kev sib cuag interfacial hauv lub cuab yeej37,38 puas tsuaj. Lub Au electrode tau raug tshem tawm thiab cov txheej spiro-OMeTAD tau ntxuav los ntawm cov substrate nrog cov kua chlorobenzene. Tom qab ntawd peb tau piav qhia txog zaj duab xis siv grazing incidence X-ray diffraction (GIXRD) (Daim Duab 5d). Cov txiaj ntsig qhia tau tias zaj duab xis tswj muaj qhov pom tseeb diffraction ncov ntawm 11.8 °, thaum tsis muaj qhov tshiab diffraction ncov tshwm sim hauv LOS qauv. Cov txiaj ntsig qhia tau tias qhov poob loj ntawm I ions hauv zaj duab xis tswj ua rau lub cim ntawm δ theem, thaum nyob hauv LOS zaj duab xis cov txheej txheem no tau raug txwv tsis pub ua.
575 teev ntawm kev taug qab MPP tas mus li ntawm lub cuab yeej tsis tau kaw hauv huab cua nitrogen thiab 1 lub hnub ci tsis muaj lub lim dej UV. ToF-SIMS kev faib tawm ntawm b I- thiab c AuI2- ions hauv LOS MPP tswj hwm lub cuab yeej thiab cov cuab yeej laus. Cov xim daj, ntsuab thiab txiv kab ntxwv sib raug rau Au, Spiro-OMeTAD thiab perovskite. d GIXRD ntawm zaj duab xis perovskite tom qab MPP xeem. Cov ntaub ntawv qhov chaw yog muab rau hauv daim ntawv ntawm cov ntaub ntawv qhov chaw.
Kev ntsuas qhov conductivity nyob ntawm qhov kub thiab txias tau ntsuas kom paub tseeb tias PbC2O4 tuaj yeem tiv thaiv kev tsiv teb tsaws chaw ntawm ion (Daim Duab Ntxiv 21). Lub zog ua kom muaj zog (Ea) ntawm kev tsiv teb tsaws chaw ntawm ion yog txiav txim siab los ntawm kev ntsuas qhov kev hloov pauv ntawm conductivity (σ) ntawm zaj duab xis FAPbI3 ntawm qhov kub thiab txias sib txawv (T) thiab siv kev sib raug zoo ntawm Nernst-Einstein: σT = σ0exp(−Ea/kBT), qhov twg σ0 yog qhov tsis hloov pauv, kB yog Boltzmann tsis hloov pauv. Peb tau txais tus nqi ntawm Ea los ntawm qhov nqes hav ntawm ln(σT) piv rau 1/T, uas yog 0.283 eV rau kev tswj hwm thiab 0.419 eV rau LOS ntaus ntawv.
Hauv kev xaus, peb muab ib lub moj khaum theoretical los txheeb xyuas txoj kev puas tsuaj ntawm FAPbI3 perovskite thiab kev cuam tshuam ntawm ntau yam tsis zoo ntawm lub zog thaiv ntawm α-δ theem hloov pauv. Ntawm cov tsis zoo no, VI tsis zoo yog kwv yees tias yuav yooj yim ua rau theem hloov pauv ntawm α mus rau δ. Ib txheej dej-insoluble thiab ruaj khov tshuaj ntawm PbC2O4 tau qhia los tswj hwm α-theem ntawm FAPbI3 los ntawm kev txwv tsis pub tsim I vacancies thiab kev tsiv teb tsaws chaw ntawm I ions. Txoj kev no txo ​​​​​​qhov sib xyaw ua ke tsis-radiative, ua rau lub hnub ci cell ua haujlwm zoo dua 25.39%, thiab txhim kho kev ruaj khov ntawm kev ua haujlwm. Peb cov txiaj ntsig muab cov lus qhia rau kev ua tiav cov formamidine PSCs zoo thiab ruaj khov los ntawm kev txwv tsis pub qhov tsis zoo-induced α rau δ theem hloov pauv.
Titanium (IV) isopropoxide (TTIP, 99.999%) tau yuav los ntawm Sigma-Aldrich. Hydrochloric acid (HCl, 35.0–37.0%) thiab ethanol (anhydrous) tau yuav los ntawm Guangzhou Chemical Industry. SnO2 (15 wt% tin (IV) oxide colloidal dispersion) tau yuav los ntawm Alfa Aesar. Lead (II) iodide (PbI2, 99.99%) tau yuav los ntawm TCI Shanghai (Tuam Tshoj). Formamidine iodide (FAI, ≥99.5%), formamidine chloride (FACl, ≥99.5%), methylamine hydrochloride (MACl, ≥99.5%), 2,2′,7,7′-tetrakis-(N , N-di-p))-methoxyaniline)-9,9′-spirobifluorene (Spiro-OMeTAD, ≥99.5%), lithium bis(trifluoromethane)sulfonylimide (Li-TFSI, 99.95%), 4-tert-butylpyridine (tBP, 96%) tau yuav los ntawm Xi'an Polymer Light Technology Company (Tuam Tshoj). N,N-dimethylformamide (DMF, 99.8%), dimethyl sulfoxide (DMSO, 99.9%), isopropyl cawv (IPA, 99.8%), chlorobenzene (CB, 99.8%), acetonitrile (ACN). Yuav los ntawm Sigma-Aldrich. Oxalic acid (H2C2O4, 99.9%) tau yuav los ntawm Macklin. Tag nrho cov tshuaj lom neeg tau siv raws li tau txais yam tsis muaj kev hloov kho lwm yam.
Cov substrates ITO lossis FTO (1.5 × 1.5 cm2) tau ntxuav nrog ultrasonically nrog detergent, acetone, thiab ethanol rau 10 feeb, thiab tom qab ntawd ziab hauv qab cov dej nitrogen. Ib txheej txheej TiO2 tuab tau tso rau ntawm FTO substrate siv cov tshuaj ntawm titanium diisopropoxybis (acetylacetonate) hauv ethanol (1/25, v/v) tso rau ntawm 500 °C rau 60 feeb. Cov SnO2 colloidal dispersion tau diluted nrog dej deionized hauv qhov ntim piv ntawm 1:5. Ntawm ib lub substrate huv kho nrog UV ozone rau 20 feeb, ib zaj duab xis nyias ntawm SnO2 nanoparticles tau tso rau ntawm 4000 rpm rau 30 vib nas this thiab tom qab ntawd preheated ntawm 150 °C rau 30 feeb. Rau perovskite precursor kua, 275.2 mg FAI, 737.6 mg PbI2 thiab FACl (20 mol%) tau yaj hauv DMF/DMSO (15/1) sib xyaw solvent. Cov txheej perovskite tau npaj los ntawm centrifuging 40 μL ntawm cov kua perovskite precursor rau saum cov txheej UV-ozone-treated SnO2 ntawm 5000 rpm hauv huab cua ib puag ncig rau 25 s. 5 vib nas this tom qab lub sijhawm kawg, 50 μL ntawm MACl IPA kua (4 mg / mL) tau poob sai sai rau ntawm lub substrate ua cov tshuaj antisolvent. Tom qab ntawd, cov yeeb yaj kiab tshiab tau annealed ntawm 150 ° C rau 20 feeb thiab tom qab ntawd ntawm 100 ° C rau 10 feeb. Tom qab txias cov yeeb yaj kiab perovskite rau chav tsev kub, H2C2O4 kua (1, 2, 4 mg yaj hauv 1 mL IPA) tau centrifuged ntawm 4000 rpm rau 30 s kom passivate qhov chaw perovskite. Ib qho tshuaj spiro-OMeTAD uas tau npaj los ntawm kev sib tov 72.3 mg spiro-OMeTAD, 1 ml CB, 27 µl tBP thiab 17.5 µl Li-TFSI (520 mg hauv 1 ml acetonitrile) tau raug txheej rau ntawm zaj duab xis ntawm 4000 rpm hauv 30 s. Thaum kawg, ib txheej Au tuab 100 nm tau raug evaporated hauv lub tshuab nqus tsev ntawm tus nqi ntawm 0.05 nm/s (0~1 nm), 0.1 nm/s (2~15 nm) thiab 0.5 nm/s (16~100 nm). ).
Kev ua tau zoo SC ntawm cov hlwb hnub ci perovskite tau ntsuas siv Keithley 2400 meter nyob rau hauv lub hnub ci simulator teeb pom kev zoo (SS-X50) ntawm lub teeb ci ntawm 100 mW / cm2 thiab tau txheeb xyuas siv cov hlwb hnub ci silicon calibrated. Tshwj tsis yog hais lwm yam, SP curves tau ntsuas hauv lub thawv hnab looj tes uas muaj nitrogen ntawm chav tsev kub (~ 25 ° C) hauv hom kev tshuaj ntsuam pem hauv ntej thiab rov qab (voltage kauj ruam 20 mV, ncua sijhawm 10 ms). Lub ntsej muag ntxoov ntxoo tau siv los txiav txim siab thaj chaw zoo ntawm 0.067 cm2 rau PSC ntsuas. Kev ntsuas EQE tau ua tiav hauv huab cua ib puag ncig siv lub kaw lus PVE300-IVT210 (Industrial Vision Technology(s) Pte Ltd) nrog lub teeb monochromatic tsom mus rau lub cuab yeej. Rau kev ruaj khov ntawm lub cuab yeej, kev sim ntawm cov hlwb hnub ci uas tsis tau kaw tau ua tiav hauv lub thawv hnab looj tes nitrogen ntawm 100 mW / cm2 siab yam tsis muaj UV lim. ToF-SIMS raug ntsuas siv PHI nanoTOFII lub sijhawm-ntawm-dav hlau SIMS. Kev ntsuas qhov tob tau txais los ntawm kev siv rab phom Ar ion 4 kV nrog thaj tsam ntawm ​​400 × 400 µm.
Kev ntsuas X-ray photoelectron spectroscopy (XPS) tau ua tiav ntawm Thermo-VG Scientific system (ESCALAB 250) siv monochromatized Al Kα (rau hom XPS) ntawm qhov siab ntawm 5.0 × 10–7 Pa. Scanning electron microscopy (SEM) tau ua tiav ntawm JEOL-JSM-6330F system. Cov duab morphology thiab roughness ntawm cov yeeb yaj kiab perovskite tau ntsuas siv atomic force microscopy (AFM) (Bruker Dimension FastScan). STEM thiab HAADF-STEM tau tuav ntawm FEI Titan Themis STEM. UV-Vis absorption spectra tau ntsuas siv UV-3600Plus (Shimadzu Corporation). Space charge limiting current (SCLC) tau kaw rau ntawm Keithley 2400 meter. Steady-state photoluminescence (PL) thiab time-resolved photoluminescence (TRPL) ntawm carrier lifetime decay tau ntsuas siv FLS 1000 photoluminescence spectrometer. Cov duab PL mapping tau ntsuas siv Horiba LabRam Raman system HR Evolution. Fourier transform infrared spectroscopy (FTIR) tau ua tiav siv Thermo-Fisher Nicolet NXR 9650 system.
Hauv txoj haujlwm no, peb siv txoj kev kuaj SSW los kawm txog txoj kev hloov pauv theem ntawm α-theem mus rau δ-theem. Hauv txoj kev SSW, kev txav mus los ntawm qhov chaw muaj zog yog txiav txim siab los ntawm kev coj ntawm hom mos mos random (qhov thib ob derivative), uas tso cai rau kev kawm ntxaws ntxaws thiab lub hom phiaj ntawm qhov chaw muaj zog. Hauv txoj haujlwm no, kev kuaj txoj kev yog ua rau ntawm 72-atom supercell, thiab ntau dua 100 thawj zaug/kawg xeev (IS/FS) khub tau sau ntawm DFT theem. Raws li IS/FS pairwise cov ntaub ntawv teeb tsa, txoj kev txuas cov qauv pib thiab cov qauv kawg tuaj yeem txiav txim siab nrog kev sib raug zoo ntawm cov atoms, thiab tom qab ntawd ob txoj kev txav mus los raws qhov chaw hloov pauv tau siv los txiav txim siab txoj kev hloov pauv xeev. (VK-DESV). Tom qab nrhiav lub xeev hloov pauv, txoj kev nrog qhov thaiv qis tshaj plaws tuaj yeem txiav txim siab los ntawm kev qeb duas cov teeb meem zog.
Tag nrho cov kev xam DFT tau ua tiav siv VASP (version 5.3.5), qhov twg cov electron-ion sib cuam tshuam ntawm C, N, H, Pb, thiab I atoms yog sawv cev los ntawm ib qho projected amplified wave (PAW) scheme. Lub exchange correlation function yog piav qhia los ntawm generalized gradient approximation hauv Perdue-Burke-Ernzerhoff parametrization. Lub zog txwv rau cov dav hlau nthwv dej tau teeb tsa rau 400 eV. Lub Monkhorst-Pack k-point grid muaj qhov loj ntawm (2 × 2 × 1). Rau txhua qhov kev teeb tsa, lattice thiab atomic positions tau optimized tag nrho kom txog thaum qhov siab tshaj plaws ntawm kev ntxhov siab qis dua 0.1 GPa thiab qhov siab tshaj plaws ntawm lub zog qis dua 0.02 eV/Å. Hauv qhov qauv nto, qhov nto ntawm FAPbI3 muaj 4 txheej, txheej hauv qab muaj cov atoms ruaj khov uas simulate lub cev ntawm FAPbI3, thiab peb txheej saum toj kawg nkaus tuaj yeem txav mus los tau yooj yim thaum lub sijhawm optimization. Cov txheej PbC2O4 yog 1 ML tuab thiab nyob rau ntawm qhov chaw I-terminal ntawm FAPbI3, qhov twg Pb khi rau 1 I thiab 4 O.
Yog xav paub ntxiv txog kev tsim txoj kev tshawb fawb, mus saib Natural Portfolio Report Abstract uas cuam tshuam nrog tsab xov xwm no.
Tag nrho cov ntaub ntawv tau txais los yog tshuaj xyuas thaum lub sijhawm kawm no suav nrog hauv tsab xov xwm luam tawm, nrog rau cov ntaub ntawv txhawb nqa thiab cov ntaub ntawv raw. Cov ntaub ntawv raw uas tau nthuav tawm hauv kev kawm no muaj nyob rau ntawm https://doi.org/10.6084/m9.figshare.2410016440. Cov ntaub ntawv qhov chaw tau muab rau tsab xov xwm no.
Green, M. et al. Cov Lus Qhia Txog Kev Ua Haujlwm ntawm Lub Hnub Ci Cell (tsab ntawv thib 57). qhov kev pab cuam. photoelectric. peev txheej. daim ntawv thov. 29, 3–15 (2021).
Parker J. et al. Tswj kev loj hlob ntawm cov txheej perovskite siv cov volatile alkyl ammonium chlorides. Xwm 616, 724–730 (2023).
Zhao Y. et al. Inactive (PbI2)2RbCl stabilizes perovskite zaj duab xis rau cov high-efficiency hnub ci cells. Science 377, 531–534 (2022).
Tan, K. et al. Cov hlwb hnub ci perovskite uas tig rov qab siv dimethylacridinyl dopant. Nature, 620, 545–551 (2023).
Han, K. et al. Ib qho crystalline formamidine lead iodide (FAPbI3): kev nkag siab txog cov qauv, kho qhov muag thiab hluav taws xob. adverb. Mathais. 28, 2253–2258 (2016).
Massey, S. et al. Kev ruaj khov ntawm theem perovskite dub hauv FAPbI3 thiab CsPbI3. AKS Energy Communications. 5, 1974–1985 (2020).
Koj, JJ, thiab lwm tus. Cov roj teeb hnub ci perovskite zoo los ntawm kev tswj hwm tus neeg nqa khoom zoo dua. Xwm 590, 587–593 (2021).
Saliba M. et al. Kev koom ua ke ntawm rubidium cations rau hauv perovskite lub hnub ci hlwb txhim kho kev ua haujlwm photovoltaic. Science 354, 206–209 (2016).
Saliba M. thiab lwm tus. Triple-cation perovskite cesium lub hnub ci hlwb: txhim kho kev ruaj khov, kev rov ua dua tshiab thiab kev ua haujlwm siab. lub zog ib puag ncig. kev tshawb fawb. 9, 1989–1997 (2016).
Cui X. et al. Cov kev nce qib tsis ntev los no hauv FAPbI3 theem stabilization hauv cov roj teeb hnub ci perovskite ua haujlwm siab Sol. RRL 6, 2200497 (2022).
Delagetta S. thiab lwm tus. Kev sib cais theem photoinduced ntawm cov sib xyaw halide organic-inorganic perovskites. Nat. sib txuas lus. 8, 200 (2017).
Slotcavage, DJ et al. Kev sib cais theem los ntawm lub teeb hauv cov halide perovskite absorbers. AKS Energy Communications. 1, 1199–1205 (2016).
Chen, L. et al. Kev ruaj khov ntawm theem intrinsic thiab intrinsic bandgap ntawm formamidine lead triiodide perovskite ib leeg siv lead ua. Anjiva. Tshuaj lom neeg. thoob ntiaj teb. Ed. 61. e202212700 (2022).
Duinsti, EA thiab lwm yam. Nkag siab txog kev rhuav tshem ntawm methylenediammonium thiab nws lub luag haujlwm hauv kev ruaj khov ntawm cov hlau lead triiodide formamidine. J. Chem. Bitch. 18, 10275–10284 (2023).
Lu, HZ et al. Kev tso pa tawm zoo thiab ruaj khov ntawm cov hlwb hnub ci dub perovskite FAPbI3. Science 370, 74 (2020).
Doherty, TAS thiab lwm yam. Cov octahedral halide perovskites ruaj khov tiv thaiv kev tsim cov theem nrog cov yam ntxwv txwv. Science 374, 1598–1605 (2021).
Ho, K. et al. Cov txheej txheem ntawm kev hloov pauv thiab kev puas tsuaj ntawm cov noob formamidine thiab cesium thiab lead iodide perovskites nyob rau hauv kev cuam tshuam ntawm cov dej noo thiab lub teeb. AKS Energy Communications. 6, 934–940 (2021).
Zheng J. et al. Kev tsim cov pseudohalide anions rau α-FAPbI3 perovskite lub hnub ci hlwb. Xwm 592, 381–385 (2021).